Activated carbon sorbent including nitrogen and methods of using the same

ABSTRACT

The present invention relates to activated carbon sorbents including nitrogen. In various embodiments, the present invention provides an activated carbon sorbent including a halogen- or halide-promoted activated carbon, the activated carbon sorbent particles including nitrogen in a surface layer of the sorbent particles. In various embodiments, the present invention provides a method of reducing the pollutant content in a pollutant-containing gas using the activated carbon sorbent. In various embodiments, the activated carbon sorbent can remove mercury from a mercury-containing gas that includes sulfur(VI) such as SO 3  more efficiently than other sorbents.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.14/195,360, filed Mar. 3, 2014, which claims the benefit of priority toU.S. Provisional Patent Application Ser. No. 61/773,549, filed Mar. 6,2013, the disclosures of which are incorporated herein in theirentireties by reference.

BACKGROUND OF THE INVENTION

Mercury (Hg) emissions have become a health and environmental concernbecause of their toxicity and ability to bioaccumulate. The U.S.Environmental Protection Agency (EPA) has issued regulations for thecontrol of mercury emissions from waste-to-energy, cement production,and coal-fired power plants. Mercury in flue gas from industrial sources(e.g., power plants) can be captured by sorbents such as activatedcarbon, which can then be removed by particulate separation devices. Theamount of standard sorbents (e.g., activated carbon) needed to serve themarket is large. Standard sorbents are not always effective and becomemore expensive as larger amounts are used.

Inhibition of mercury capture from gas streams by active carbon sorbentscan occur when sulfur(VI) (e.g. SO₃, H₂SO₄) is present in the gasstream, with increasing inhibition at higher concentrations. Mercurycapture above sulfur(VI) concentrations of 3 ppm by mole is limited.Many utilities desire to operate SO₃ injection systems at a minimum ofabout 5-6 ppm to improve ash conectability. However, a sulfur(VI)concentration of about 6 ppm can diminish elemental mercury capture byabout 25%-50% or more. With this reduction, it becomes difficult, if notimpossible, to economically achieve desired mercury levels. Thescientific understanding of why a severe inhibition of mercury sorptionexists when sulfur(VI) concentrations increase by such a small amount islimited.

SUMMARY OF THE INVENTION

In various embodiments, the present invention provides an activatedcarbon sorbent. The activated sorbent includes a halogen- orhalide-promoted carbon. The activated carbon includes activated carbonsorbent particles including nitrogen. The concentration of nitrogen in asurface layer of the sorbent particles is at least one of 1) higher thanthe concentration of nitrogen in a core of the sorbent particles and 2)higher than the concentration of nitrogen in the carbon material fromwhich the sorbent particles are derived.

In various embodiments, the present invention provides a method ofmaking an activated carbon sorbent. The method includes contacting acarbonaceous material and a nitrogenous material, to provide anunpromoted carbon sorbent comprising nitrogen. The method also includespromoting at least a portion of the unpromoted sorbent by contacting theportion of the unpromoted sorbent with a promoter to form an activatedcarbon sorbent comprising activated carbon sorbent particles comprisingnitrogen, wherein the concentration of nitrogen in the sorbent particlesis higher than the concentration of nitrogen in the carbonaceousmaterial.

In various embodiments, the present invention provides an activatedcarbon sorbent for use in mercury removal from a mercury-containing gas.The activated carbon sorbent includes a halogen- or halide-promotedinorganic activated carbon particles including nitrogen in a surfacelayer of the sorbent particles. The nitrogen atoms are at sufficientconcentration in the surface layer of the activated carbon sorbentparticles to at least one of a) decrease neutralization by HSO₃ ¹⁻ orSO₃ ²⁻ of carbocations in the activated carbon sorbent, as compared to acorresponding activated carbon sorbent comprising less or substantiallyno nitrogen in a corresponding particle surface layer undersubstantially similar conditions, and b) at least partially blockcarbocations in the activated carbon from forming ionic bonds with HSO₃¹⁻ or SO₃ ²⁻, as compared to a corresponding activated carbon sorbentincluding less or substantially no nitrogen in a corresponding particlesurface layer under substantially similar conditions.

In various embodiments, the present invention provides a method ofreducing the pollutant content in a pollutant-containing gas. The methodincludes obtaining or providing an activated carbon sorbent includingactivated carbon sorbent particles including nitrogen in a surface layerof the sorbent particles. The method includes contacting apollutant-containing gas with the activated carbon sorbent. Thecontacting forms a pollutant-sorbent composition. The method alsoincludes separating at least some of the pollutant-sorbent compositionfrom the pollutant-containing gas. The separating gives a separated gas.

In various embodiments, the present invention provides a method forreducing the mercury content of a mercury-containing gas. The methodincludes obtaining or providing a carbon precursor. The carbon precursorincludes nitrogen. The method includes obtaining or providing asubstrate material. The method includes contacting the carbon precursorand the substrate material. The contacting provides an inorganicmatrix-supported sorbent starting material. The method includes heatingthe inorganic matrix-supported sorbent starting material. The heatingprovides an unpromoted sorbent. The method includes promoting at least aportion of the unpromoted sorbent by contacting (e.g., chemicallyreacting) the portion of the unpromoted sorbent with a promoter to forma promoted inorganic matrix-supported activated carbon sorbent. Theactivated carbon sorbent includes activated carbon sorbent particlesincluding nitrogen in a surface layer of the sorbent particles. Themethod includes contacting the mercury-containing gas with the activatedcarbon sorbent. The contacting forms a mercury-sorbent composition. Themethod also includes separating at least some of the mercury-sorbentcomposition from the mercury-containing gas. The separating gives aseparated gas. The concentration of sulfur(VI) in the mercury-containinggas is about 3-1000 ppm by mole. A first quantity of the activatedcarbon sorbent forms a mercury-sorbent composition at a first mercuryadsorption rate. The first adsorption rate is higher than a mercuryabsorption rate of the first quantity of a corresponding activatedcarbon sorbent including at least one of a) less or substantially nonitrogen in a corresponding particle surface layer, b) less orsubstantially no halide- or halogen-promotion, and c) less orsubstantially no inorganic matrix support.

In various embodiments, the present invention provides a method ofmaking an activated carbon sorbent. The method includes obtaining orproviding an unpromoted carbon sorbent including nitrogen. The methodincludes promoting at least a portion of the unpromoted sorbent bycontacting (e.g., chemically reacting) the portion of the unpromotedsorbent with a promoter to form an activated carbon sorbent includingactivated carbon sorbent particles including nitrogen in a surface layerof the sorbent particles.

Various embodiments of the present invention provide certain advantagesover other activated carbon sorbents and methods of using the same, atleast some of which are unexpected. In some embodiments, the activatedcarbon sorbent can separate a material (e.g., a pollutant) from a gasthat includes that material more efficiently than other methods. Invarious embodiments, mercury removal efficiencies of the activatedcarbon exceed or match that of conventional methods with added benefitssuch as reduced costs. The method and materials of various embodimentsof the present invention can operate more efficiently than other methodsof mercury removal. In some embodiments, the method and materials ofvarious embodiments can remove a given amount of mercury for a smalleramount of financial expenditure, as compared to other methods. Forexample, the method and materials of various embodiments can remove alarger amount of mercury for a given mass of carbon, as compared toother methods of removing mercury, including as compared to othermethods of removing mercury that include a carbon sorbent.

For example, in some embodiments, a given mass of thenitrogen-containing activated carbon sorbent can absorb mercury from amercury-containing gas stream including sulfur(VI) (e.g., SO₃, H₂SO₄, orthe like), such as greater than about 3 ppm sulfur(VI), such as about3-200 ppm sulfur (VI), 3-1000 ppm sulfur(VI), or about 3-10 ppmsulfur(VI), at a higher rate than the same mass of a correspondingactivated carbon sorbent including less or no nitrogen, such as a lowerconcentration of nitrogen or no nitrogen in a corresponding particlesurface layer. In some embodiments, carbocations in the activated carbonsorbent are neutralized less by ions derived from SO₃, such as SO₃ ²⁻ orHSO₃ ¹⁻, than other activated carbon sorbents, such as other activatedcarbon sorbents including less or substantially no nitrogen in acorresponding particle surface layer. In some embodiments, carbocationsin the activated carbon sorbent are at least partially blocked from ionsderived from SO₃, such as SO₃ ²⁻ or HSO₃ ¹⁻, more than in otheractivated carbon sorbents, such as in other activated carbon sorbentsincluding less or substantially no nitrogen in a corresponding particlesurface layer.

In some embodiments, the sorbent can be regenerated and reused, reducingdisposal of spent sorbents and decreasing the cost of mercury removal.In some embodiments, preparation or promotion of the activated carbonsorbent can advantageously occur on site. On site preparation andpromotion can have advantages including, for example: reduction orelimination of equipment costs and operating costs of a separatepreparation facility or location, reduction or elimination oftransportation costs, fresher and more reactive sorbent, reduction ofhandling, on-site tailoring of composition (such as when changing fuelsor reducing loads).

In some embodiments, counter to traditional teachings that inorganiccomponents can hinder sorption of pollutants on activated carbon, aninorganic matrix support in the sorbent can enhance the sorption ofpollutant in the activated carbon, such as on a proximate andoxidatively reactive carbon graphene layer. In various embodiments, aninorganic matrix support can stabilize the development of cationic siteson the proximate graphene carbon structures which can oxidize pollutantssuch as mercury. In embodiments that include an inorganicmatrix-supported nanocomposite that is promoted via a hydrogen halidecompound obtained from degradation or reaction of the correspondingammonium halide, another advantageous role for the inorganic portion canbe in providing a binding site for the ammonia that is released fromeither the decomposition or reaction of the ammonium salt. The boundammonia can form a complex with basic character that can react with SO2or SO3 in the pollutant-containing gas and can prevent theirinterference with the sorption of pollutants such as mercury in or nearactive sites on the activated carbon.

Clays are usually difficult to filter or separate from an aqueousmedium. In some embodiments that include clay as an inorganic matrixsupport, the clay is advantageously stabilized to dispersion in anaqueous medium, and can be easily separated from an aqueous medium byfiltration.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to certain embodiments of thedisclosed subject matter. While the disclosed subject matter will bedescribed in conjunction with the enumerated claims, it will beunderstood that the exemplified subject matter is not intended to limitthe claims to the disclosed subject matter.

Values expressed in a range format should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. For example, arange of “about 0.1% to about 5%” or “about 0.1% to 5%” should beinterpreted to include not just about 0.1% to about 5%, but also theindividual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g.,0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range.The statement “about X to Y” has the same meaning as “about X to aboutY,” unless indicated otherwise. Likewise, the statement “about X, Y, orabout Z” has the same meaning as “about X, about Y, or about Z,” unlessindicated otherwise.

In this document, the terms “a,” “an,” or “the” are used to include oneor more than one unless the context clearly dictates otherwise. The term“or” is used to refer to a nonexclusive “or” unless otherwise indicated.In addition, it is to be understood that the phraseology or terminologyemployed herein, and not otherwise defined, is for the purpose ofdescription only and not of limitation. Any use of section headings isintended to aid reading of the document and is not to be interpreted aslimiting; information that is relevant to a section heading may occurwithin or outside of that particular section. Furthermore, allpublications, patents, and patent documents referred to in this documentare incorporated by reference herein in their entirety, as thoughindividually incorporated by reference. In the event of inconsistentusages between this document and those documents so incorporated byreference, the usage in the incorporated reference should be consideredsupplementary to that of this document; for irreconcilableinconsistencies, the usage in this document controls.

In the methods of manufacturing described herein, the steps can becarried out in any order without departing from the principles of theinvention, except when a temporal or operational sequence is explicitlyrecited. Furthermore, specified steps can be carried out concurrentlyunless explicit claim language recites that they be carried outseparately. For example, a claimed step of doing X and a claimed step ofdoing Y can be conducted simultaneously within a single operation, andthe resulting process will fall within the literal scope of the claimedprocess.

Definitions

The term “about” as used herein can allow for a degree of variability ina value or range, for example, within 10%, within 5%, or within 1% of astated value or of a stated limit of a range.

The term “substantially” as used herein refers to a majority of, ormostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%,98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.

The term “number-average molecular weight” as used herein refers to theordinary arithmetic mean of the molecular weight of individual moleculesin a sample. It is defined as the total weight of all molecules in asample divided by the total number of molecules in the sample.Experimentally, the number average molecular weight (M_(n)) isdetermined by analyzing a sample divided into molecular weight fractionsof species i having n_(i) molecules of molecular weight M_(i) throughthe formula M_(n)=ΣM_(i)n_(i)/Σn_(i). The number average molecularweight can be measured by a variety of well-known methods including gelpermeation chromatography, spectroscopic end group analysis andosmometry.

The term “weight-average molecular weight” as used herein refers(M_(w)), which is equal to ΣM_(i) ²n_(i)/ΣM_(i)n_(i), where n_(i) is thenumber of molecules of molecular weight M_(i). In various examples, theweight average molecular weight can be determined using lightscattering, small angle neutron scattering, X-ray scattering, andsedimentation velocity.

The term “solvent” as used herein refers to a liquid that can dissolve asolid, liquid, or gas. Nonlimiting examples of solvents are silicones,organic compounds, water, alcohols, ionic liquids, and supercriticalfluids.

The term “air” as used herein refers to a mixture of gases with acomposition approximately identical to the native composition of gasestaken from the atmosphere, generally at ground level. In some examples,air is taken from the ambient surroundings. Air has a composition thatincludes approximately 78% nitrogen, 21% oxygen, 1% argon, and 0.04%carbon dioxide, as well as small amounts of other gases.

The term “room temperature” as used herein refers to a temperature ofabout 15° C. to 28° C.

As used herein, “mineral” refers to a naturally occurring solid chemicalsubstance formed through biogeochemical processes, having, for example,characteristic chemical composition, highly ordered atomic structure,and specific physical properties.

Description

In various embodiments, the present invention provides an activatedcarbon sorbent and associated method for reduction of mercury contentfor use in combustion systems that have inherently high levels ofsulfur(VI) (e.g. as SO₃, or related compounds that can be derivedtherefrom such as H₂SO₄ or other sulfates) in the flue gas and for usein plants that use SO₃ injection for ash conditioning for improved ashcollection. The method can obtain high mercury capture rates in a highsulfur(VI)-content flue gas by, in some examples, overcoming the kineticand equilibrium effects that can inhibit mercury capture in high SO₃ orhigh-sulfate (e.g. high sulfur(VI)) systems. The activated carbonsorbent includes activated carbon sorbent particles. The concentrationof nitrogen in a surface layer of the sorbent particles can be higherthan the concentration of nitrogen in a core of the sorbent particles.In some examples, the activated carbon sorbent can be promoted.

In various embodiments, the activated carbon sorbent and associatedmethod can be effective for removal of elemental mercury vapor in an airor flue gas stream at moderate temperatures (e.g., about 25-330° C., orabout 50-500° C.). In some examples, the activated carbon is notimpregnated with sulfur or metal halides, which can be unstable athigher temperatures.

In some embodiments, the removal process does not involve adsorption ofthe elemental mercury like that occurring at low temperatures, but caninvolve the catalyzed reaction of mercury with an oxidant to form anorganomercury compound that includes the mercury bound to the activatedcarbon surface, wherein the mercury can be released via, e.g., reactionwith acid, to provide a mercury (II) species with low vapor pressuressuch as mercury sulfate, mercury bromide, or mercury chloride. The ionicmercury(I) form can be an oxide or salt of an optional acid used in theprocess (such as sulfate from sulfuric acid), which can have lowervolatility. The activated carbon can exhibit a high rate of oxidativecatalytic activity due to, for example, numerous active catalytic sitesand, at the same time, possess a large surface area for generation ofthe organomercury compound and thus rapidly generate the convertedmercury(II) salt.

Activated Carbon Sorbent Including Nitrogen.

In various embodiments, the present invention provides an activatedcarbon sorbent. The activated carbon sorbent can include halogen- orhalide-promoted activated carbon particles; in other embodiments, theactivated carbon sorbent is not promoted. In some examples, theactivated carbon can have an inorganic matrix-support.

The activated carbon sorbent can include activated carbon sorbentparticles. The concentration of nitrogen in a surface layer of thesorbent particles can be at least one of 1) higher than theconcentration of nitrogen in a core of the sorbent particles and 2)higher than the concentration of nitrogen in the activated carbonmaterial from which the activated carbon sorbent particle was derived.The surface layer of each particle can independently be continuous(e.g., unbroken, with minimal or no gaps) or non-continuous. The surfacelayer can be at the outer surface of the particle. The surface layer ofeach particle can independently have any suitable thickness. The surfacelayer can have a variable thickness, or can have a substantiallyconsistent thickness. In some embodiments, the surface layer can have athickness of about 0.000,001% to about 99.99% of the radius of theparticle, 0.001% to 99%, 0.001% to about 50%, 1% to about 50%, 0.1% to25%, or about 25% to 50% of the radius of the particle. If the particleis non-spherical the radius can be estimated as about one-half of thelargest dimension of the particle.

In some embodiments, each activated carbon particle can independentlyinclude about 1.001 times higher nitrogen concentration in the surfacelayer than in the core or less, or about 1.01, 1.1, 1.2, 1.4, 1.6, 1.8,2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 50, 100, or about 1000 times highernitrogen concentration in the surface layer than in the core. In someembodiments, the concentration of nitrogen in the surface layer can beabout 0.000,001 wt % or less, or about 0.001 wt %, 0.01 wt %, 0.1 wt %,1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 10 wt %, 15 wt %, 20 wt %, 30 wt%, 40 wt %, 50 wt %, 60 wt %, 70 wt %, 80 wt %, or about 90 wt % or morenitrogen. In some examples, the concentration of nitrogen in the surfacelayer can be about 0.001 wt %-99 wt % nitrogen, 5 wt %-80 wt %, or about5-60 wt %. In various embodiments, the concentration of nitrogen in thecore can be about 0 wt %, 0.000,001 wt %, or about 0.001 wt %, 0.01 wt%, 0.1 wt %, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 10 wt %, 15 wt %,20 wt %, 50 wt %, or 90 wt % or more. In some examples, theconcentration of nitrogen in the core can be about 0.001 wt %-99 wt %nitrogen, 0.1 wt %-20 wt %or about 1 wt %-6 wt %.

The activated carbon sorbent can be in any suitable form. For example,the activated carbon can be granular, or fine particles. The activatedcarbon can have any suitable shape, such as spherical or irregular. Theactivated carbon can have an average diameter of about 0.1 nm or less,or about 1 nm, 10 nm, 100 nm, 1 μm, 10 μm, 100 μm, 1 mm, or about 10 mmor more. In some examples, the activated carbon has a diameter of about0.01 μm or less, or about 0.1 μm, 1μm, 2 μm, 3 μm, 4 μm, 5 μm, 10 μm, 20μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 1000 μm ormore. In some examples, the diameter of the particle is about 0.1-1000μm, or 1-100 μm, or about 1-30 μm. If a particle is non-spherical, thediameter can be estimated as the longest dimension of the particle. Theabsorption capacity of the activated carbon sorbent including mercurycan be about 0.000,1 mg mercury per gram of sorbent or less, or about0.001 mg/g, 0.01, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45,50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 150, 200, 300400, 500 750, or about 1 g mercury per gram of sorbent or more.

In some embodiments, at least some of the carbon in the activated carbonis in the graphene form of carbon. The graphene form of carbon can, insome embodiments, include higher concentrations of locations suitable asactive sites. In some examples, certain parts of graphene carbon canhave the highest concentrations of locations suitable as active sites:in some examples at the edges, in some examples in non-edge locations.Such locations suitable as active sites may be activated via treatmentwith halide or halogen, as described herein. In various embodiments, thecarbon in the activated carbon sorbent can be at least about 1 wt %, 2wt %, 3 wt %, 4 wt %, 5 wt %, 10 wt %, 20 wt %, 30 wt %, 40 wt %, 50 wt%, 60 wt %, 70 wt %, 80 wt %, 90 wt %, 95 wt %, 96 wt %, 97 wt %, 98 wt%, 99 wt %, 99.9 wt %, 99.99 wt %, or more than about 99.999 wt %graphene form of carbon.

In some embodiments, the nitrogen is substantially homogenouslydistributed throughout the activated carbon particles. In someembodiments, the nitrogen is substantially homogenously distributed inthe core of the activated carbon sorbent particles; in otherembodiments, the nitrogen can have any suitable distribution in thecore. In some embodiments, the nitrogen is substantially homogenouslydistributed in the surface layer of the activated carbon sorbentparticles. In some embodiments, the nitrogen in the surface layer is nothomogeneously distributed; e.g., the nitrogen can have a gradient withthe highest concentration at the outside of the surface layer and alower concentration at an inside of the surface layer.

The nitrogen can be in any suitable form within the activated carbon. Insome examples, the nitrogen can be a nitrogen atom bound to one or morehydrogen atoms or one or more other atoms that are, for example,carbon-containing groups that are part of the activated carbon framework(e.g. the activated carbon backbone or appendages thereof), or to anorganic group. In some examples, for example, the nitrogen can beneutral or can bear a positive charge (e.g. ammonium) or a negativecharge. The nitrogen can have any suitable oxidation state, for examplezero or one. The nitrogen can be bound to 4, 3, 2, 1, or zero hydrogenatoms. The nitrogen can be bound to one or more activated carbonframeworks at zero, 1, 2, 3, or 4 locations. In some embodiments, thenitrogen can include one or two double bonds or one triple bond to thecarbon framework of the activated carbon or to other functional groups,such that the nitrogen is bound to 1, 2, or 3 carbon atoms.

The nitrogen in the activated carbon can be derived from any nitrogencontaining compound, such as a nitrogen-containing organic or inorganiccompound, such as by pyrolysis or carbonization. In some examples, thenitrogen is derived from or part of any nitrogen-containing heterocycle,or from any other nitrogen-containing compound. For example, thenitrogen can be derived from indole, quinoxaline, carbazole,isoquinoline, piperazine, quinolone, quinoxaline, diazabicyclooctane,polyacrylonitrile, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetatecopolymer, vinylpyrrolidone-acrylic acid copolymer,vinylpyrrolidone-maleic acid copolymer, polyethylenimine, an amino acid(e.g., alanine, arginine, asparagine, aspartic acid, cysteine,glutamine, glutamic acid, glycine, histidine, isoleucine, leucine,lysine, methionine, phenylalanine, proline, serine, threonine,tryptophan, tyrosine, or valine), analine, nitrobenzene, hydroxylamine,urea, hydrazine, sulfamic acid, nitriles, carbamates, isocyanates,urethanes, or a combination thereof In some examples, the nitrogen inthe activated carbon can be derived from or part of anitrogen-containing inorganic compound, such as ammonia, ammoniumbromide, ammonium chloride, nitric acid, nitrous acid, nitrogen dioxide,compounds including NO₃, compounds including NO₂, and the like.

In various embodiments, the nitrogen-containing activated carbon sorbentcan absorb pollutants such as mercury at a higher rate in a givenconcentration of sulfur(VI) than other sorbents. In some examples, afirst quantity of the activated carbon sorbent forms a mercury-sorbentcomposition at a first mercury adsorption rate in a gas compositionincluding mercury wherein the concentration of sulfur(VI) in the gascomposition is about 3-2000 ppm by mole, where the first adsorption rateis higher than a mercury absorption rate of the first quantity of acorresponding activated carbon sorbent including at least one of a) less(e.g., lower concentration) or substantially no nitrogen in acorresponding particle surface layer, b) less or substantially nohalide- or halogen-promotion, and c) less or substantially no inorganicmatrix support.

The mechanism of operation of the activated carbon sorbent is notintended to be limited to any particular theory of operation as advancedherein. In some embodiments, the nitrogen in the surface layer at leastpartially decreases neutralization by SO₃ (or ions or other materialsderived from SO₃ such as HSO₃ ¹⁻ or SO₃ ²⁻) of carbocations in theactivated carbon sorbent, as compared to a corresponding activatedcarbon sorbent including less or substantially no nitrogen in acorresponding particle surface layer under substantially similarconditions. In some examples, the nitrogen in the surface layer at leastpartially blocks carbocations in the activated carbon from forming ionicbonds with SO₃ (or ions or other materials derived from SO₃ such as HSO₃¹⁻ or SO₃ ²⁻), as compared to a corresponding activated carbon sorbentincluding less or substantially no nitrogen in a corresponding particlesurface layer under substantially similar conditions.

In various active carbon sorbents, two issues can occur during pollutantcapture such as mercury capture: 1) getting high oxidation reactivity ata carbon edge site (kinetic effect) and 2) preventing/avoiding the lossof oxidized mercury from the carbon-bound states as a result ofdisplacement by sulfate (equilibrium effect). Elemental mercury in thegas phase can be oxidized at the carbon edge surface (cationic zigzagsites) and can be bound covalently as an organomercury halide. Thecationic sites can be formed by addition of acids or halogens (X₂) tothe carbon edge structure, which can result in a carbenium-halide ionpair. The oxidation can be assisted by the negative halide ionstabilizing the developing positive charge on the mercury atom as itadds to the carbenium atom. The oxidation can occur more readily if theoxidation potential (charge) of the carbenium ion or stability thereofis higher, which can be influenced or determined by the adjacent chargespresent in the carbon framework structure and nearby surroundings.Additional cationic functionality in the structure can raise theoxidation potential (increases positive charge) at the reactive site, orcan increase the stability of a positive charge at the reactive site.Negative groups (such as ions derived from SO₃, e.g., SO₃ ² ⁻ and SO₂¹⁻, can stabilize and lower the overall charge and available carbeniumions and thereby reduce the reactivity for oxidation of the mercury andavailability for capture of mercury.

The longer-term equilibrium effect can be less important for captureover a short contact time, such as inflight capture by electrostaticprecipitators (ESPs). However, in some situations the equilibriumdisplacement problem can be more important, e.g., baghouse collection orSO₃ injection or formation in a selective catalytic reduction (SCR)unit. Since sulfate concentrations can increase with time of exposure onthe carbon surface, their effect in displacing mercury halides into thegas phase (desorption and breakthrough) can be important in longexposure times. When SO₃ related compounds and ions such as sulfuricacid, sulfate, or related ions, are initially present or form quickly ona wet surface, e.g., with SO₃ injection, the equilibrium displacementeffect can also become important in systems with a short contact time.

In various embodiments, the nitrogen in the surface layer can stabilizeor increase positive charge in the carbon structure which can overcomedepletion of charge by sulfate and the carbon edge can be promoted witha halogen/halide. In some embodiments, the collection of cationiccenters in the carbon edge structures (normally present in a halogenated(e.g. brominated) carbon and useful for rapid mercury oxidation) can beimpaired by interference of bisulfate ions and other related ions formedfrom SO₃ reaction at the carbon surface. These anions can neutralize thepositive charge of the carbenium ions and lower the overall oxidationpotential of the remaining reactive sites that have a shared charge.Additional cationic centers can be generated within the carbon structureby introducing nitrogen atoms during the activated carbon formation,helping to counter this effect and offset some of the charge that canused by ionic or other interactions with, e.g., SO₃ or ions derived fromSO₃. Atoms such as nitrogen can be added in the polycyclic structure toform increased cations or to stabilize existing cations.

In some embodiments, the nitrogen in the surface layer of the activatedcarbon sorbent particles increases the cationic charge in the sorbentbecause the nitrogen protects the cation centers from SO₃ and ions orcompounds derived from SO₃. The nitrogen atoms can form or be part of acharged cage or other protective blocking structure around a carbon edgestructure to prevent access by SO₃ and ions or compounds derived fromSO₃ such as anionic sulfate groups but allow diffusion of mercury atomsinto the nanostructure to reach active centers for oxidation or sorbtion

In some embodiments, an inorganic matrix support such as clay can helpto block active cationic centers from access by SO₃ and ions orcompounds derived from SO₃ or can help to stabilize or increase thecationic charge in the active carbon sorbent.

In some embodiments, addition of acid or acidic materials to theactivated carbon improves the performance. In various embodiments, acidor acidic materials can be added prior to the use of the carbon byimpregnating an acidic solution into the carbon, or can be added as asolution or gas to the sorbent bed during use. The modified carbon canbe impregnated with an acidic material, such as about 1 wt % or less orabout 2 wt %, 3, 4, 5, 6, 7, 8, 9, 10, 15, or about 20 wt % or more oracidic material, such as HBr, HCl, H₂SO₄, and the like.

Method of Reducing Pollutant Content in a Pollutant-Containing Gas.

In various embodiments, the present invention provides a method of usingthe activated carbon sorbent. The method can be any suitable method. Forexample, some embodiments provide a method of reducing the pollutantcontent in a pollutant-containing gas. In some examples, thepollutant-containing gas can include at least some oxygen. The methodcan include obtaining or providing an activated carbon sorbent includingactivated carbon sorbent particles including nitrogen in a surface layeror the sorbet particles. In some embodiments, the concentration ofnitrogen in a surface layer of the sorbent particles can be higher thanthe concentration of nitrogen in a core of the sorbent particles. Theactivated carbon sorbent can be any activated carbon sorbent includingnitrogen described herein. In some examples, the activated carbonsorbent including nitrogen can be a promoted activated carbon sorbentincluding nitrogen. In some examples, the activated carbon sorbentincluding nitrogen can be an inorganic matrix-supported or nanocompositeactivated carbon sorbent including nitrogen. In some examples, theactivated carbon sorbent can be both promoted and an inorganicmatrix-supported or nanocomposite activated carbon sorbent includingnitrogen. In some embodiments, the activated carbon sorbent can bepromoted but include no inorganic matrix support. In some embodiments,the activated carbon sorbent can be neither promoted nor inorganicmatrix-supported. The activated carbon sorbent can include binding sitesthat can bind with at least one of the pollutant in thepollutant-containing gas and an oxidized species of the pollutant, toform the pollutant-sorbent composition. At least a portion of thebinding sites in the activated carbon sorbent can react with at leastone of the pollutant and an oxidized species of the pollutant, to formthe pollutant-sorbent composition.

The method of reducing the pollutant content in a pollutant-containinggas can include contacting a pollutant-containing gas with the activatedcarbon sorbent. The contacting forms a pollutant-sorbent composition.The contacting can be any suitable contacting. in some embodiments,contacting the pollutant-containing gas with the activated carbonsorbent can include adding or injecting the activated carbon sorbentinto the pollutant containing gas. For example, the contacting can occurin the gas. In another embodiment, the contacting can occur in anaqueous liquid. In another example, the contacting can occur in the gas,and subsequently contacting can also occur in an aqueous phase such as ascrubber.

In some embodiments, during the contacting of the pollutant-containinggas with the activated carbon sorbent, the activated carbon sorbent canbe in any suitable configuration such that it contacts thepollutant-containing gas. For example, during the contacting, theactivated carbon sorbent can be at least one of in a fixed structuresuch as a fixed bed, in a moving structure such as a moving bed, in ascrubber, in a filter (e.g., a fixed filter or a travelling/movingfilter) or suspended in the pollutant-containing gas.

The pollutant-sorbent composition can be any suitable compositionincluding the pollutant or an oxidized or otherwise chemicallytransformed form of the pollutant and the activated carbon sorbent. Insome embodiments, mercury is absorbed in its elemental form by thesorbent; the mercury-sorbent composition can include the sorbent and theelemental form of mercury. In some embodiments, the mercury is convertedby the sorbent via a chemical reaction, such as oxidation, such that themercury from the gas is transformed into an organomercury compoundincluding the carbon framework of the activated carbon bound to mercury,which can be released as a mercury (II) compound upon reaction with asuitable acid to generate the salt thereof In some embodiments, themercury-sorbent composition can include at least one of elementalmercury, organomercury compound, and Hg(II) compounds.

In some examples, elemental mercury or transformed mercury can remainabsorbed to the sorbent until the mercury-sorbent composition has beenremoved in a later separation step. For example, elemental mercury ortransformed mercury can be absorbed, or reacted and absorbed, into oronto the sorbent composition, such that after separating thepollutant-sorbent composition from the pollutant-containing gas, theseparated gas has about 1% or less, 3%, 5%, 10%, 20%, 30%, 40%, 50%,60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.9%, 99.99%, or about99.999% or more of the mercury that was originally present in thepollutant-containing gas. In some embodiments, elemental mercury ortransformed mercury can be released from the mercury-sorbentcomposition; for example, less than about 1 wt %, 3 wt %, 5 wt %, 10 wt%, 20 wt %, 30 wt %, 40 wt %, 50 wt %, 60 wt %, 70 wt %, 80 wt %, 90 wt%, 95 wt %, or less than about 99 wt % of the mercury can be releasedfrom the mercury-sorbent composition prior to separation of themercury-sorbent composition from the gas. In some examples, the majorityof absorbed elemental or transformed mercury can remain part of themercury-sorbent composition until the mercury-sorbent composition isremoved in a later separation step. In some examples, transformedmercury that is released from the mercury-sorbent composition can belater removed from the gas via the separation step or another step. Insome examples, elemental or transformed mercury that has been releasedfrom the mercury-sorbent composition can contact activated carbonsorbent to form a mercury-sorbent composition, to be removed later viathe separation step.

The method of reducing the pollutant content in a pollutant-containinggas can include separating at least some of the pollutant-sorbentcomposition from the pollutant-containing gas, to give separated gas. Insome embodiments, separating at least some of the pollutant-sorbentcomposition from the pollutant containing gas includes separating in aparticulate separator. The particulate separator can be any suitableparticulate separator, such as an electrostatic precipitator (ESP), abaghouse, a wet scrubber, a filter, cyclone, fabric separator, or anycombination thereof In some embodiments, an electrostatic precipitatorcan be used, followed by a scrubber. In other embodiments, anelectrostatic precipitator can be used without a scrubber, or anotherparticulate separator can be used. Some devices that can function asparticulate separators can also have other functions, for example ascrubber can also remove SO2 or SO₃. In embodiments that includecontacting of the mercury with a sorbent in an aqueous phase, e.g. in ascrubber, the removal of mercury from the gas that occurs within theaqueous phase by reaction or interaction of the mercury with the sorbentin the aqueous phase can be considered separation of the mercury-sorbentcomposition from the gas.

In some examples, by separating the particulates from themercury-containing gas, at least about 20 wt %, 30 wt %, 40 wt %, 50 wt%, 60 wt %, 70 wt %, 80 wt %, 90 wt %, 95 wt %, 96 wt %, 97 wt %, 98 wt%, 99 wt %, 99.9 wt %, 99.99 wt %, or about 99.999 wt % or more mercurycan be removed from the mercury-containing gas stream. As discussedherein, the mercury can be removed in the form of elemental mercury, orin the form of a transformed mercury, such as an organomercury compoundincluding the mercury bound to the carbon framework of the activatedcarbon or as Hg(II) complexed with a suitable counterion.

In some embodiments, at least one of the contacting and the separatingoccurs in an aqueous scrubber. The aqueous scrubber can be any suitableaqueous scrubber. For example, the scrubber can include an aqueousslurry that includes the activated carbon sorbent.

In some embodiments, the method removes about 1% or less, or about 2%,3, 4, 5, 10, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96,97, 98, 99, 99.5, 99.9, 99.99, 99.999, or about 99.9999% or more of themercury present in the mercury-containing gas (e.g. the finalconcentration of mercury divided by the initial concentration ofmercury). In some embodiments, the activated carbon sorbent combineswith about 50-100 wt % of the mercury present in the mercury-containinggas, or about 60-90 wt %, 60-80 wt %, 70-80 wt %, 80-90 wt %, 90-100 wt%, or about 95-100 wt % or the mercury present in the mercury-containinggas.

In some embodiments, the concentration of sulfur(VI) in themercury-containing gas (e.g. from SO₃, H₂SO₄, and the like) is greaterthan about 3 ppm (by mole) and a first quantity of the activated carbonsorbent forms a mercury-sorbent composition at a first mercuryadsorption rate, wherein the first adsorption rate is higher than amercury absorption rate under substantially similar conditions of thefirst quantity of a corresponding activated carbon sorbent including atleast one of a) less or substantially no nitrogen in a correspondingsurface layer, b) less or substantially no halide- or halogen-promotion,and c) less or substantially no inorganic matrix support. In someembodiments, the concentration of SO₃ in the pollutant-containing gas ator near the location wherein the pollutant-containing gas contacts thesorbent is about 1 ppm to about 100,000 ppm, 2-10,000 ppm, 3 ppm-000ppm, 3-100 ppm, 3-50 ppm, 3-10 ppm, or about 3-6 ppm or more, or theconcentration of sulfur(VI) in the pollutant-containing gas (e.g. fromSO₃, H₂SO₄, and the like) at or near the location wherein thepollutant-containing gas contacts the sorbent is about 1 ppm to about100,000 ppm, 2-10,000 ppm, 3 ppm-1000 ppm, 3-100 ppm, 3-50 ppm, 3-10ppm, or about 3-6 ppm or more, wherein ppm designates parts per millionby mole. The concentration can be an instantaneous concentration, or anaverage concentration over time. The nitrogen in the surface layer ofthe activated carbon sorbent particles can decrease neutralization ofcarbocations in the activated carbon by at least one of SO₃ ²⁻ and HSO₃¹⁻, as compared to a corresponding activated carbon sorbent includingless or substantially no nitrogen in a corresponding surface layer undersubstantially similar conditions. The nitrogen in the surface layer ofthe activated carbon sorbent particles can at least partially blockcarbocations in the activated carbon from at least one of SO₃ ²⁻ andHSO₃ ¹⁻, as compared to a corresponding activated carbon sorbentincluding less or substantially no nitrogen in a corresponding particlesurface layer under substantially similar conditions.

In some embodiments, the method of reducing the pollutant content in apollutant-containing gas includes at least one of during and prior tothe contacting adding or injecting an alkaline component into thepollutant-containing gas. The alkaline component can be any suitablealkaline component, such as an oxide, hydroxide, carbonate, or phosphateof an alkali element, an alkali or alkaline-earth element, and acompound or material including the same. In various examples, theaddition of an alkaline component separately or with the carbon sorbentcan result in improved mercury capture. Various factors can impact theeffectiveness of the alkaline addition, such as, for example, flue gaspollutants, flue gas constituents (e.g., SO₂, NO_(x), Se, HCl, and thelike), operating temperature, mercury form, and mercury concentration.In some examples, the alkaline-to-activated-carbon ratio can be adjustedto optimize for a given set of site conditions.

In some embodiments, the activated carbon includes a stabilizing agent.In some examples, the stabilizing agent can include at least one of S,Se, H₂S, SO₂, H₂Se, SeO₂, CS₂, P₂S₅, or mixtures thereof. Thestabilizing agent can be added before or after promotion.

In various embodiments, the rate of mercury removal can decreasegradually with increasing temperature and with increased loading ofmercury, at least partially due to the increase in the rate of a reversereaction. In some examples, the highest rates can occur at about 100 to150° C., 50-200° C., or about 50-250° C. In some examples, at 400° C.,the reverse reaction can be highly favored thermodynamically. in someexamples, the activated carbon can be regenerated by washing with waterto remove sulfuric acid thereon, such as described in U.S. Pat. No.8,173,566.

In some embodiments, the method of reducing the pollutant content in apollutant-containing gas can include regenerating the pollutant-sorbentcomposition to give a regenerated activated carbon sorbent. Theregeneration can be any suitable regeneration that allows theregenerated activated carbon sorbent to be reused for removing pollutantfrom the pollutant-containing gas. The method can include using theregenerated activated carbon sorbent to remove the pollutant from thepollutant-containing gas.

Method of Making Activated Carbon Including Nitrogen.

In some embodiments, the activated carbon including activated carbonparticles including nitrogen is commercially acquired. In otherembodiments, the activated carbon including nitrogen is synthesized. Forexample, the method of reducing the pollutant content in apollutant-containing gas can include making an activated carbonincluding nitrogen.

For example, in the method of reducing the pollutant content in apollutant-containing gas, obtaining or providing the activated carbonsorbent can include obtaining or providing a carbon precursor includingnitrogen. The method can also include processing (e.g., heating) thecarbon precursor, to provide the activated carbon sorbent. Theprocessing can include any suitable processing. In methods that includeheating the carbon precursor, the method can include any other suitableoptional step in addition to the heating, such as washing, chemicaltreatment, or vibration. In some embodiments, the carbon precursorincludes a carbonaceous material including carbon and a nitrogenousmaterial including nitrogen. The heating can include heating to about100° C. to 15,000° C., 200° C. to 10,000° C., 300° C. to 9000° C., orabout 400° C. to 8000° C.

The carbonaceous material can be any suitable carbonaceous material. Forexample, the carbonaceous material can be an organic compound. In someexamples, the carbonaceous material includes at least one of brownsugar, barley sugar, caramel, cane sugar, corn syrup, starch, molasses,molasses raffinate (sugar waste product), glucans, galactans, xylans,and a sugar waste product. In some examples, the carbonaceous materialincludes powdered activated carbon, granular activated carbon, carbonblack, carbon fiber, carbon honeycomb or plate structure, aerogel carbonfilm, pyrolysis char, or an activated carbon or regenerated activatedcarbon with a mass mean particle size greater than fly ash in a flue gasstream to be treated. The nitrogen can be derived from or part of can beany suitable nitrogenous material. For example, the nitrogenous materialcan be a nitrogen-containing organic compound, such as anitrogen-containing heterocycle. In some examples, the nitrogenousmaterial includes indole, quinoxaline, carbazole, isoquinoline,piperazine, quinolone, quinoxaline, diazabicyclooctane,polyacrylonitrile, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetatecopolymer, vinylpyrrolidone-acrylic acid copolymer,vinylpyrrolidone-maleic acid copolymer, polyethylenimine, an amino acid(e.g., alanine, arginine, asparagine, aspartic acid, cysteine,glutamine, glutamic acid, glycine, histidine, isoleucine, leucine,lysine, methionine, phenylalanine, proline, serine, threonine,tryptophan, tyrosine, or valine), analine, nitrobenzene, hydroxylamine,urea, hydrazine, sulfamic acid, nitriles, carbamates, isocyanates,urethanes, or a combination thereof. The nitrogenous material can be anysuitable ammonium salt, such as an ammonium salt derived from analiphatic nitrogen-containing compound, an aromatic amine-containingcompound, or a heterocyclic nitrogen-containing compound; in embodimentswherein the nitrogenous material is a halide salt, the activated carbonincluding nitrogen perform equivalently to an promoted material and apromotion step can be skipped or reduced. In some examples, thenitrogenous material can be at least one of ammonia, ammonium bromide,ammonium chloride, nitric acid, nitrous acid, nitrogen dioxide,compounds including NO3, compounds including NO₂, and the like.

In one example, the activated carbon including activated carbon sorbentparticles including nitrogen can be prepared by surface modification ofany kind of activated carbon or char by applying a nitrogen-containingpolymer coating or impregnation to the existing carbon or lowertemperature char and recarbonizing the impregnated carbon. The coatingor impregnation can include a polymer or copolymer containing a nitrogenheterocycle such as a polymerized vinylpyrollidone. In one example ofthis type of carbon, poly(vinylpyrrolidone),poly(vinylpyrrolidone-co-maleic acid) or poly(vinylpyrrolidone-covinylacetate) is used to coat the carbon surface. Upon heating orrecarbonization, the impregnated mixture can form a nitrogen-containingactivated carbon surface layer on the particles. Thenitrogen-concentration in the surface layer of the nitrogen-containingactivated carbon can be higher than the nitrogen concentration of thematerial prior to the surface modification or impregnation withnitrogen.

In one example, the activated carbon including nitrogen can be preparedby surface modification of an oxidized char by treatment of the charwith a suitable nitrogenous compound, such as ammonia or urea, followedby activation of the nitrogen-impregnated material.

In one example, the activated carbon including nitrogen can be preparedby impregnation of nitrogen containing compounds into a char followed bycarbonization and activation of the impregnated char by conventionmethods. One example carbon of this type is the combination of amines oramino acids with carbohydrates, which combination undergoes the Mai:Hardcondensation reaction on heating to form carbon surface containingnitrogen heterocyclics.

In one example, the activated carbon including nitrogen can be preparedby impregnation of a nitrogen containing compound into a coal, lignite,or leonardite, followed by carbonization and activation.

Promoted Activated Carbon Sorbent Including Nitrogen.

In some embodiments, the activated carbon including activated carbonsorbent particles including nitrogen includes a promoted activatedcarbon sorbent including nitrogen. The activated carbon sorbentincluding nitrogen used in the method of reducing the pollutant contentin a pollutant-containing gas can be a promoted activated carbonsorbent, and can include nitrogen. The method can include promoting anunpromoted activated carbon sorbent, or the promoted sorbent can becommercially acquired.

For example, the method of reducing the pollutant content in apollutant-containing gas can include obtaining or providing anunpromoted carbon sorbent. The unpromoted carbon sorbent can be anysuitable unpromoted sorbent including nitrogen, and can be synthesizedor commercially acquired. The method can include obtaining or providinga promoter. The method can include promoting at least a portion of theunpromoted sorbent by contacting (e.g., chemically reacting) the portionof the unpromoted sorbent with the promoter to form the activated carbonsorbent.

The promoter can be any suitable promoter, such that a promoted sorbentis formed that is effective for the removal of pollutants such asmercury from a pollutant-containing gas. For example, the promoter caninclude a halogen or halide promotor. The halogen or halide can befluorine or fluoride, chlorine or chloride, bromine or bromide, oriodine or iodide. In some examples, the promotor can include at leastone of a halogen, a Group V halide, a Group VI halide, a hydrogenhalide, an ammonium halide, an alkali earth metal halide, and analkaline earth metal halide. Thus, the activated carbon in someembodiments can be at least one of halogen-promoted, Group Vhalide-promoted, Group VI halide-promoted, hydrogen halide-promoted,ammonium halide-promoted, alkali earth metal halide-promoted, andalkaline earth metal halide-promoted. The promoter can include at leastone of HI, Mr, ICl NH₄Br, NaBr, CaBr₂, HBr, NaCl, CaCl₂, and HCl. Insome examples, the promoter is NH₄Br, and can be injected into a warmzone in a duct, for example separately or with the activated carbonsorbent. In some examples, any suitable halogen- or halide-containingmaterial, such as NaCl, CaCl₂, NaBr, or CaBr₂ can be injected with thecoal during the combustion process, which can activate the carbon. Invarious embodiments, the halogen- or halide-containing material cantransform into an activate promotor such as active bromide or chloridecompounds like HCl, HBr, xCl, or xBr. In some examples, the promoter isin a form including at least one of a vapor form, in a solvent, as aliquid, as a solid, and a combination thereof In some embodiments, thepromoting can occur in an aqueous scrubber, wherein the scrubberincludes an aqueous slurry that includes the promotor.

The promoting of the sorbent material can occur before addition orinjection into a gas stream, during addition or injection into a gasstream, after addition or injection into a gas stream, or a combinationthereof, wherein the gas stream can be a mercury-containing gas stream,a transport stream, or a combination thereof In some examples, thepromoter can be added to the sorbent before the promoter and the sorbentreact, such that the heat of the gas stream into which the promoter isadded causes the promoting of the sorbent. For example, the promoter canbe added as a gas, as a gas dissolved in a liquid, or as a solid such asa salt, or other substance (e.g., acid) dissolved in liquid (e.g.,water), for example, hydrobromic acid. In examples wherein the promoteris added in a liquid such as water, the water can be allowed to dry,which can allow the promoter to adhere to, impregnate, or react with theactivated carbon sorbent, or a combination thereof In some examples, apre-added promoter can be an ammonium salt, such as an ammoniumchloride, an ammonium bromide, or an ammonium iodide, including, forexample, mono-, di-, tri-, or tetraalkyl ammonium halides, or NH₄ ⁺halide salts. In some examples, the promoter can be added to the sorbentnear to or at the time of promoting; for example, the promoter can beadded to a gas stream with the sorbent or such that it contacts thesorbent within a heated gas stream, such as a mercury-containing gasstream or a feed gas stream. In some examples, the promoter can beNH₄Br.

In some embodiments, a promoter precursor transforms into the halogen orhalide promoter that reacts with the activated carbon sorbent to givethe activated carbon material. The promoter precursor can be anysuitable precursor that can transform into the halogen or halidepromoter. In some embodiments, the promoter precursor can be at leastone of on the unpromoted sorbent and added or injected with theunpromoted sorbent. In some embodiments, the promoter can be HBr, and insome examples, the HBr can be provided via degradation or reaction of apromoter precursor such as ammonium bromide, sodium bromide, or calciumbromide. The promoter can be HCl, and in some examples, the HCl can beprovided via degradation or reaction of a promoter precursor such asammonium chloride, sodium chloride, or calcium chloride. The promotercan be HF, and in some examples, the HF can be provided via degradationor reaction of a promoter precursor such as ammonium fluoride, sodiumfluoride, or calcium fluoride. In some examples, the promoter (e.g., HBror HCl) or promoter precursor (e.g., NH₄Br, NaBr, CaBr₂, NH₄C₁, NaCl,CaCl₂) can be added or injected in the flue gas separately from theactivated carbon sorbent or with the activated carbon sorbent (e.g., canbe applied to the sorbent pre-injection, added or injectedsimultaneously at the same location, or added or injected simultaneouslyat different locations). In some examples, NaCl, CaCl2, NaBr, or CaBr2can be added with uncombusted material such as uncombusted coal.

Inorganic Matrix-Support or Nanocomposites.

In some embodiments, the activated carbon including activated carbonparticles including nitrogen includes an inorganic matrix-support or isa nanocomposite. The activated carbon including nitrogen used in themethod of reducing the pollutant content in a pollutant-containing gascan include an inorganic matrix-support or can be a nanocomposite. Themethod can include adding an inorganic matrix-support to the activatedcarbon or making a nanocomposite using unsupported activated carbonincluding nitrogen, or the method can include commercially acquiring thematrix-supported or nanocomposite activated carbon. In variousembodiments, the inorganic matrix support includes at least one ofdiatomaceous earth, a clay, a zeolite, or a mineral.

For example, the method of reducing the pollutant content in apollutant-containing gas can include obtaining or providing a substratematerial. The substrate material can be any suitable substrate. Forexample, the substrate can be at least one of diatomaceous earth, aclay, a zeolite, or a mineral. The method can include contacting thecarbon precursor and the substrate material, to provide a sorbentstarting material. The contacting can take place in any suitablefashion. The contacting mixes the carbon precursor and the substratematerial, such that when the conglomeration is heated (or subjected toany other suitable source of energy), the carbon nanocomposite orsupported sorbent is formed. The contacting can be performed such thatthe carbon precursor is approximately evenly distributed on thesubstrate. In some examples, water or another solvent can be added tohelp distribute the carbon precursor on the substrate. In examples wherewater is included in the mixture of the carbon precursor and thesubstrate, the conglomeration can be dried prior to the heating. Thedrying can occur in any conventional manner (e.g., convective,conductive, microwave, and the like), including by heating near or abovethe boiling point of the solvent, in the case of water (e.g., 50°C.-120° C. or higher), at atmospheric pressure, under pressure, or undera vacuum.

The substrate can include any suitable porous material. For example, thesubstrate material can be diatomaceous earth, zeolites, porous minerals(e.g., clays) including, for example, smectites (e.g., montmorillonite,bentonite, nontronite, saponite), kaolins, illites, chlorites,sepiolite, or attapulgites. In some examples, the substrate can includepolymers, non-metals, metals, metalloids, ceramics or mixtures, andblends, as well as composites and alloys thereof. The materials can besynthetic or naturally occurring or naturally derived materials.Examples of synthetic polymers include any common thermoplastics andthermosetting materials. Examples of metals include aluminum, titanium,copper, steel, and stainless steel. Examples of ceramics include anyform of alumina, zirconia, titania, and silica. Examples of naturallyoccurring or naturally derived materials include wood, wood composites,paper, cellulose acetate, and geologic formations such as granite orlimestone. Examples of non-metals include various forms of carbon suchas graphite or carbon. Examples of metalloids include silicon orgermanium. The porous material can be a construction material such asconcrete or asphalt.

In some examples, the substrate material can be present in from about 1wt % to about 99 wt %, about 20 wt % to about 80 wt %, or about 40 wt %to about 60 wt % of the starting material for the carbon nanocompositesorbent. Wt% in this paragraph refers to the percentage by weight basedon the total weight of the carbon precursor and the substrate material.

The method can include processing (e.g., heating, vibrating, sonicating,microwaving, or otherwise adding energy to) the sorbent startingmaterial, to provide the activated carbon sorbent. The contactedcomposition of the carbon precursor and the substrate can then beprocessed (e.g., heated, vibrated, sonicated, microwaved, or othersuitable addition of energy) to form the carbon nanocomposite orinorganic matrix-supported sorbent. The processing can take place at anysuitable temperature, such that the sorbent is sufficiently formed, forexample heating to about 50° C., 100° C., 200° C., 300° C., 400° C.,500° C., 600° C., 700° C., 800° C., 900° C., 1000° C., 1100° C., orabout 1200° C. or higher. The processing can take place for any suitabletime, such that the carbon nanocomposite is sufficiently formed, forexample, greater than about 1 min, 2 min, 5 min, 10 min, 30 min, 1 h,1.5 h, 2 h, 3 h, 4 h, 5 h, 10 h, or greater than about 24 h. The heatingcan take place in any suitable apparatus, for example, a unit thatsubstantially excludes oxygen, e.g., that allows heated inert gas air toflow around the mixture being heated. In one example, the heating occursin a furnace having an inert gas environment therein. The processing canbe accelerated, or lengthened, depending on the apparatus and thenanocomposite or supported material.

In some embodiments, heating the sorbent starting material can provide asecond sorbent starting material. The method can further includereacting the second sorbent starting material with an acidic or basicmaterial, to provide the activated carbon sorbent. The acidic or basicmaterial can be any suitable acidic or basic material, such as HBr, HCl,H₂SO₄, KOH, NaOH, and the like. In some embodiments, treatment with anacidic or basic material can prepare the activated carbon for treatmentwith a promotor or can prepare the material such that sufficientreactivity or absorption with mercury or another pollutant is obtained.

Method of Making an Active Carbon Sorbent Including Nitrogen.

In various embodiments, the present invention provides a method ofmaking an activated carbon sorbent including activated carbon sorbentparticles including nitrogen. Embodiments of the present invention caninclude any activated carbon sorbent including nitrogen made by themethod. The method includes obtaining or providing unpromoted sorbentincluding nitrogen. The unpromoted sorbent including nitrogen can be anysuitable activated carbon sorbent including nitrogen, such as anyactivated carbon sorbent including nitrogen described herein. Theunpromoted sorbent including nitrogen can be acquired commercially orcan be synthesized. The method can include promoting at least a portionof the unpromoted sorbent. The promoting can include contacting (e.g.,chemically reacting) the portion of the unpromoted sorbent with apromoter to form an activated carbon sorbent including activated carbonsorbent particles including nitrogen.

In some examples, the unpromoted sorbent including nitrogen can includean inorganic matrix support or can be a nanocomposite. For example, themethod of making an activated carbon sorbent including nitrogen caninclude obtaining or providing a carbon precursor including nitrogen.The method can include obtaining or providing a substrate material. Themethod can include contacting the carbon precursor and the substratematerial to provide a sorbent starting material. The method can alsoinclude heating the sorbent starting material to provide the unpromotedcarbon sorbent including nitrogen. The unpromoted sorbent includingnitrogen can include activated carbon sorbent particles includingnitrogen.

In some embodiments, the method of making an activated carbon sorbentincluding nitrogen can include synthesizing the carbon precursorincluding nitrogen from carbonaceous and nitrogenous materials. Forexample, the method can include obtaining or providing a carbonaceousmaterial including carbon and a nitrogenous material including nitrogen.The method can include suitably contacting and processing thecarbonaceous material and the nitrogenous material, wherein processingcan including at least one of heating, microwaving, sonication,vibration, and the like, to provide the carbon precursor includingnitrogen.

EXAMPLES

The present invention can be better understood by reference to thefollowing examples which are offered by way of illustration. The presentinvention is not limited to the examples given herein.

Example 1 Impregnation of Nitrogen Precursors Into a Char Followed byCarbonization and Activation of the Impregnated Char Example 1a CarbonPrecursor

A carbon (20×60 mesh) prepared by steam activation of a lignite char wasstirred with an aqueous solution of dextrose and ethanolamine in ratioof 1 part of carbon to 0.016 parts of ethanolamine and 0.034 parts ofdextrose. The water solvent was removed by rotovaporation and theimpregnated carbon was air-dried. The dried material was reactivated at750° C. for 2 hours under nitrogen stream.

Example 1b Char Precursor

A char (20×60 mesh)prepared by heating a lignite at 400° C. was stirredwith an aqueous solution of dextrose and ethanolamine in ratio of 1 partof carbon to 0.016 parts of ethanolamine and 0.034 parts of dextrose.The water solvent was removed by rotovaporation and the impregnatedcarbon was air-dried. The dried material was activated at 750° C. for 2hours under nitrogen stream,

Example 1c Wood Charcoal Precursor

A carbon (20×60 mesh) prepared by steam activation of a wood char wasstirred with an aqueous solution of dextrose and ethanolamine in ratioof 1 part of carbon to 0.016 parts of ethanolamine and 0.034 parts ofdextrose. The water solvent was removed by rotovaporation and theimpregnated carbon was air-dried. The dried material was reactivated at750° C. for 2 hours under nitrogen stream.

Example 1d Wood Charcoal—Alanine

A carbon (20×60 mesh)prepared by steam activation of a wood char wasstirred with an aqueous solution of dextrose and alanine in ratio of 1part of carbon to 0.016 parts of ethanolamine and 0.034 parts ofalanine. The water solvent was removed by rotovaporation and theimpregnated carbon was air-dried. The dried material was reactivated at750° C. for 2 hours under nitrogen stream.

Example 2 Tube Reactor Testing

The molecular sieve carbons obtained as described in Examples 1a-d wereimpregnated with 5 wt % of sulfuric acid. The impregnated carbon wasthen dried in an oven at 110° C. The carbon (0.100 g) was packed into a3 mm diameter pyrex tube and held in place by glass wool plugs at bothends. A constriction in the pyrex tube at exit end prevented the plugfrom blowing out. The reactor tube was heated in a GC oven at 150°C.±0.50 as a constant temperature device. The mercury vapor wascontained in an air flow of 100 cm³/min through the reactor tube at aconcentration of 429-447 micrograms/m³, determined with a continuousmercury vapor monitor.

The mercury source was a temperature-calibrated permeation tube. Thepermeation tube was heated in a double-jacketed glass condenser with acirculating hot silicone oil system. The concentration in the effluentair stream from the reactor tube was monitored with a continuouscold-vapor UV mercury vapor monitor (EPM). Blank runs were conductedbefore each carbon test to determine the mercury concentration. Theinstrument was zeroed with an air stream passed through a large iodizedcarbon filter. This apparatus thus gave the percent of mercury notremoved by the carbon bed (the concentration of mercury in the outletdivided by the concentration of mercury in the inlet, times 100). Forthe nitrogenous molecular sieve carbons (examples 1-4) only 1% of themercury vapor was not removed by the carbon bed over a period of severalhours.

Example 3 Filter Bed Testing

The sorbent carbon pretreated as in Example le was ground to about 200mesh and introduced into a tube where it could be drawn by reducedpressure onto a teflon or quartz filter held in a stainless steelholder. The carbon-impregnated filter and holder were then placed in theoven under air flow and tested as described in Example 2.

Example 4 Impregnation of Nitrogen-Containing Polymers Into an ActivatedCarbon or Char Followed by Carbonization and Activation of theImpregnated Material Example 4a Vinylpyrrolidone-Acrylic Acid Copolymer

A carbon prepared by steam activation of a lignite was stirred with anaqueous solution of poly(vinylpyrrolidone-co-acrylic acid) for 30 min.The amount of the polymer was selected to provide loadings of 1% to 30%by weight. The solvent was evaporated by rotovaping at 50° C. andfurther dried in an oven at 110° C. The impregnated carbon wasreactivated by heating at 750° C. for 2 hours in a stream of nitrogen.Approximately 40% of the polymer weight was converted to surface coatingand 60% was volatilized.

Example 4b Vinylpyrrolidone-Vinyl Acetate Copolymer

An activated carbon was impregnated with poly(vinylpyrrolidone-co-vinylacetate) dissolved in dichloromethane. The solvent was evaporated andthe impregnated carbon died in an oven at 110° C. The impregnated carbonwas then activated by heating at 750° C. for 2 hours in a nitrogenstream.

Example 4c Poly(Vinylpyrrolidone)

An activated carbon was impregnated with one of poly(vinylpyrrolidone)and the copolymers described in Examples 4a-b and activated as describedin Example 4a.

Example 4d Poly(Vinylpyrrolidone)

A KOH-activated lignite was impregnated with one of polyvinylpyrrolidoneand the copolymers described in Examples 4a-4b and activated asdescribed in Example 4a.

Example 4e Wood-Derived Charcoa

Wood-derived charcoal was impregnated with one of poly(vinylpyrrolidone)and the copolymers described in Examples 4a-4b and activated asdescribed in Example 4a.

Example 4f Carbonization of a Lignite. (Hypothetical Example)

Chars are produced by carbonization of a lignite, impregnated by one ofpoly(vinylpyrrolidone) and the copolymers described in Examples 4a-4b,and. activated as described in Example 4a. As an alternative, steamactivation can be used.

Example 4g Steam Activation

Examples 4a-4e were carried out using steam activation of the carbonmaterial impregnated with nitrogen-containing polymers to generateeffective sorbents.

Example 5 Impregnation of Nitrogen Precursors Into a Coal, Lignite, orLeonardite, Followed by Carbonization and Activation of the ImpregnatedMaterial. Example 5a 1,4-Diazabicyclo[2.2.2]Octane (DABCO)

Lignite (as received) was stirred with an aqueous solution of DABCO in aratio of 1 part of coal to 0.02 parts of DABCO. The water solvent wasremoved by filtration, and the impregnated coal was air-dried. The driedmaterial was carbonized at 400° C. and activated at 750° C. for 2 hoursunder a nitrogen stream.

Example 5b Sulfamic Acid

Lignite (as received) was stirred with an aqueous solution of sulfamicacid in a ratio of 1 part of coal to 0.02 parts of sulfamic acid. Thewater solvent was removed by filtration, and the impregnated coal wasair-dried. The dried material was carbonized and activated at 750° C.for 2 hours under a nitrogen stream.

Example 5c Carbonized Lignite

Lignite was carbonized at 400° C. for 30 minutes, and the resulting charwas treated by stirring with sulfamic acid solution as described inExample 5b. The treated char was then activated as described in Example5b.

Example 5d Steam Activation

Steam activation of the DABCO or sulfamic acid-impregnated chars wasalso effective in producing mercury sorbent carbons.

Example 6 Preparation of Nitrogen-Containing Pitches

Nitrogen-containing pitches were prepared using a procedure reported byMochida et al. (Mochida, I.; An, K. H.; Korai, Y. Carbon 1995, 33,1069). Preparations are summarized in Table 1. As an example, a mixtureof isoquinoline (26 g, 0.2 mole), anhydrous aluminum(III) chloride (13.3g, 0.25 mole), and nitrobenzene (7.68 g, 0.06 mole) was placed in atwo-necked flask equipped with a reflux condenser and a nitrogen inlettube. The mixture was refluxed at 280° C. for 4 hours. The residue wasextracted with 0.1 N hydrochloric acid and filtered. The residue waswashed with 0.1 N hydrochloric acid. The residue was further extractedwith methanol to remove any monomer. The methanol-insoluble pitch wasdried in vacuo. The yield of the pitch was 49%. A portion of thenitrogen-containing pitches were carbonized using Procedure A or B in anitrogen stream, as described in Example 7.

TABLE 1 Preparation of nitrogen-containing pitches. Substrate CatalystCocatalyst Temperature Yield Soluble (g, mole) (g, mole) (g, mole) (°C.) Time (hr) (g, %) (%) Indole None None 253* 4  9.6 Methanol (10,0.77) (96%) (100) Quinoxaline AlCl₃ Nitrobenzene 225* 4 13.5 EDA** (26,0.2) (13.3, 0.1) (7.68, 0.06) (52%) Carbazole AlCl₃ Nitrobenzene 25 1259.1 EDA** (16.7, 0.1) (27.7, 0.2) (3.6, 0.03) (92%) Isoquinoline AlCl₃Nitrobenzene 280  4  6.5 EDA** (26, 0.2) (13.3, 0.1) (7.68, 0.06) (25%)*indicates reactions carried out in 300-mL Parr reactor. **indicatesethylenediamine.

Several modifications of the method were utilized for the quinolinepolymerization. in addition to the flask method, a Parr reactor was usedfor the reaction, and temperatures and reaction times were varied. Theyields are reported in Table 2. In this procedure, 64.5 g of quinolineand 33.25 g of aluminum(III) chloride were placed in a 300-mL Parrautoclave. The reactor was sealed under nitrogen and heated at 280° C.for 4 hours. The hard black mass was extracted with 0.1 N hydrochloricacid followed by extraction with methanol and drying in vacuo. In orderto determine the solubility of the polymer, a 10-g portion of this blackmass was extracted with 100 mL of ethanol. Extraction data showed that27 wt % of the product dissolved in ethanol.

TABLE 2 Preparation of nitrogen-containing pitches. Quinoline AlCl₃ TimeYield Ethanol-S Ethanol-I (g) (g) Temp. (° C.) (hr) (g, %) (g) (g) 64.533.25 280 12 57.7 — — (89%) 64.5* 33.25 175 12 0 — — (0%) 64.5* 33.25280 12 59.1 — — (92%) 64.5* 33.25 280 4 56.8 7.3** 2.7 (88%) (73%) (27%)*indicates reactions carried out in 300-mL Parr reactor. **indicates 10g of pitch was extracted with ethanol.

Example 7 Preparation of Nitrogen-Impregnated Carbon

Impregnations and recarbonizations were performed to investigate theeffects of precursor concentration, activation procedure, and sorbentparticle size on mercury sorption. The precursor base carbon, granularactivated carbon (Calgon F400 or Gascoyne AC, 20×60) was impregnatedwith various nitrogen-containing polymers and pitches using an incipientwetness method, described below. For the fine-particle sorbent tests influe gas compositions, the Calgon carbon was ground to about a 400 meshsize prior to impregnation. The nitrogen polymers such asvinylpyrrolidone polymers and copolymers are commercially available. Theurea, alanine-dextrose, piperazine-dextrose, andpolyethylenimine-dextrose compositions were prepared similarly.

In a typical procedure for the incipient wetness method, the desiredamount of polymer or pitch dissolved in an appropriate solvent was addedto the carbon slowly with thorough mixing. The paste was dried to removesolvent. The dried product was packed in a stainless steel tube andactivated in a gentle flow of nitrogen using procedure A or procedure B.

Procedure A included: Heated from 25° C. to 400° C. at 10° C./min; heldat 400° C. for 30 min; heated from 400° to 750° C. at 20° C./min; andheld at 750° C. for 4 hr.

Procedure B included: Heat from 25° C. to 225° C. at 15° C./min; heatedfrom 225° C. 270° C. at 1° C./min; held at 270° C. for 1 hr; cooled toroom temperature; heated up to 750° C. at 15° C./min; and held at 750°C. for 4 hr.

Example 8 Preparation of Nitrogen-Containing Carbons From InsolubleFractions

Insoluble fractions of pitches described in Table 1 were converted intonitrogen-containing carbons by heating in a gentle flow of nitrogenusing Procedure B as described above. The resulting carbons were porousglassy materials, similar to cokes.

Example 9 Preliminary Screening of Sorbents Made Using the NitrogenContaining Materials of Examples 6-7 for Mercury Capture Example 9aSimulation of the Sulfuric Acid Accumulation

Capture of SO₃ and subsequent sulfuric acid formation on the surface ofthe nitrogen containing carbons in the hot flue gas stream was simulatedby adding 5 wt % sulfuric acid by the incipient wetness method. Theacid-impregnated carbons were dried at 110° C.

Example 9b Packed-Bed Tests

Packed-bed tests in airflow were conducted on the granular carbonproducts to evaluate the effects of surface modification. The mercurysorption was tested in a flow-through tubular reactor system equippedwith continuous in-line mercury analysis of the effluent from the bed todetermine mercury removal rates as a function of time. Integration ofbreakthrough volumes allows determination of mercury sorption per unitmass carbon (mg/g). Air with an elemental mercury concentration of 56 or81 μg/m³ was passed through the heated (150° C.) reactor. To obtain thisconcentration, the mercury source was placed in a double-jacketed glasscondenser and heated to the desired temperature by pumping hot oilthrough the condenser.

A glass tube with constriction and glass wool plug was used as thereactor for the mercury sorption tests. A gas chromatography (GC) ovenwas used as a constant temperature (150° C.) chamber for the reactor.Before the actual test, a blank test was run. The glass tube wasattached to the source and the mercury analyzer by Teflon tubes. Mercuryvapors diluted with air (2000-4000 cm³/min or 4-8 scfh measured at thedetector end) were passed through the tube. The mercury analyzer(Environmental and Process Monitoring [EPM] continuous vapor monitor)was interfaced to a Hydra and personal computer (PC) to record the data.For the packed-bed tests, impregnated activated carbons (20×60-meshsize) were used. In an actual test, about 0.2-0.6 g of sorbent waspacked in the glass tube and held by glass wool plugs on both ends. Thetests were conducted with a source temperature of 150° C., an oventemperature of 150° C., and an airflow=4 or 8 scfh (4000 cm³/min).Numerous tests were performed at 4000 cm³/min (8 scfh) with carbonsprepared by impregnation of various nitrogen compounds, polymers, andpitches into a base Calgon carbon (Tables 3 and 4). These conditionsgave partial breakthroughs for the sorbents and allowed comparisons oftheir kinetic activities.

TABLE 3 Sorbent testing of surface-treated carbons for mercury removalat 8 scfh. Airflow = 4000 cm³/min (8 scfh), over temperature = 150° C.,mercury concentration = 81 μg/m³. % Hg removed (time, min)Recarbonization H₂SO₄ End of Carbon source method Impregnation Initial50% test Blank —  0 <1 —  (0) Calgon 5% 87 50 38  (0) (171)  (304) Calgon/urea A 5% 95 50 49  (0) (305)  (306)  EERC*/urea A 5% 100  50 38 (0) (575)  (1221)  Calgon/2% sulfamic acid A 5% 92 50 39  (0) (226) (1303)  Calgon/5% PVP A 5% 94 50 42  (0) (2217)  (2574)  Calgon/10% PVPA 5% 88 50 55  (0) (150)  (253)  Calgon/10% PVP A 5% 90 50 65  (0)(300)  (1098)  Calgon/5% PVP A 5% 98 50 43  (0) (3315)  (4010) Calgon/2% PVP A 5% 79 50 49  (0) (312)  (320)  Calgon/10% PVP A 5% 85 5030  (0) (424)  (1114)  Calgon/5% vinylpyrrolidone-vinyl A 5% 90 50 39acetate copolymer  (0) (84) (180)  Calgon/5% vinylpyrrolidone-acrylic A5% 90 50 29 acid copolymer  (0) (76) (362)  Calgon/5%vinylpyrrolidone-acrylic A 5% 98 50 50 acid copolymer  (0) (223)  (223) Calgon/polyethylenimine A 5% 88 50 22  (0) (373)  (1147) Calgon/dextrose + polyethylenimine A 5% 88 50 35  (0) (51) (350) Calgon/dextrose + alanine A 5% 88 50 53  (0) (76) (216) Calgon/dextrose + piperazine A 5% 65 50 25  (0) (35) (942)  *indicatesthat the activated carbon was prepared in Example 4a.

TABLE 4 Sorbent testing of nitrogenous pitch-impregnated carbons formercury capture. Recarbonization procedure B was used for all samples.Sorbent = 0.20 g, particle size = 20 × 50 mesh, airflow = 8 scfh (4000mL/min), source temperature = 150° C., oven temperature = 150° C.Mercury Concen- % Hg removed File H₂SO₄ tration (time, min) name Sorbent(g) (wt %) (μg/m³) Initial 50% Final RKS32 None — 81 —  50 —  <1 RKS35Calgon/5 wt % 5% — 89  50  49 quinolone*  (0) (306)  (308) RKS23Calgon/5 wt % 5% — 91  50  46 quinolone*  (0) (204)  (292) RKS37Calgon/5 wt % 5% — 90  50  25 quinoxaline  (0) (632) (1300) RKS31Calgon/5 wt % 5% — 90  54  34 isoquinoline  (0) (584) (1214) RKS75Calgon/5 wt 5% — 98  50  49 % indole  (0) (1403)  (1473) *indicatespitch obtained from heating quinolone and aluminum (III) chloride inParr reactor was dissolved in ethanol and impregnated on Calgon carbon.**indicates pitch obtained from refluxing of quinolone with aluminum(III) chloride was dissolved in EDA and impregnated on Calgon carbon.

Example 9c Test Results

Carbons prepared by impregnation of urea or sulfamic acid into theCalgon base carbon and recarbonization gave initial capture rates of 95%or 92%, respectively. These results are significantly better than thoseobserved with the unmodified Calgon carbon. Testing the urea carbon atlower temperature (75° C.) gave 100% initial capture. Carbons preparedby impregnation of a nitrogen-containing polymer were highly active inthese tests. The sorbent prepared by impregnation of 5 wt % PVP andactivated using procedure A (fast heating rate) demonstrated superioractivity. The initial removal was 94%, and the decrease to 50% removalrequired 2217 min. Thus this sorbent retains its high activity farlonger than the urea carbon. The sorbent prepared using 10% PVP (alsoProcedure A) was less active (initially 88% removal, decreasing to 50%at 150 min

Using procedure B (slower heating rate) gave more active sorbent at the10% PVP concentration level. Another set of carbons was prepared withdifferent concentrations using Procedure B. Again, the impregnation with5% concentration of PVP resulted in high activity (initially 98%removal, decreasing to 50% at 3315 mm). The 10% PVP was again lessactive, and the 2% PVP concentration was the least active.

The carbons prepared from the copolymers of PVP were also prepared andevaluated. The copolymer with vinyl acetate (PVPcoVA) impregnated at 5%concentration (Procedure A) gave a sorbent with relatively low activity.The poly(vinylpyrrolidone-co-acrylic acid) (PVPcOAA) at 5% also gave alow activity sorbent. Using Procedure B for activation improved theactivity slightly.

Another type of N-polymer-impregnated carbon was prepared usingpolyethylenimine. This polymer precursor contains nitrogen in thepolymer backbone, in contrast to the PVP where the nitrogen is attachedto the carbon chain backbone. The activity was similar to that of the10% PVP polymers.

Several carbons were prepared by impregnating mixtures of dextrose andamines. None of these exhibited high activities in these tests. Previoustests showed that the dextrose +alanine-impregnated carbon (Procedure B)was fairly active. Since Procedure A was used in the present study,decreases in activity might be related to the fast heating rate used. Itmay be quite beneficial to perform the reaction slowly in preparingsorbents from these precursors.

The sorbents prepared by impregnation of the nitrogenous pitchesprepared by polymerization of various heterocyclics were all fairlyactive (Table 4), but significant differences in activity were observed.The N-carbon prepared from impregnation of quinoxaline pitch was 2-3times more active than the quinoline-derived N-carbon. The activity ofthe isoquinoline-derived carbon was also very high. The high activity ofthe indole-derived carbon was also of great interest. It is an importantlead since indoles are more readily available than the quinoxalineprecursors.

Testing was also conducted on the carbonized pitches prepared from theinsoluble fractions of the nitrogenous pitches. The activities of thecarbonized pitches were very poor. Initial breakthrough was substantial,with percent removals of 21% to 54%, possibly related to the glassynature of the carbonized pitches. Although the surface areas were notdetermined, they may be very low, since the materials did not resembleactivated carbons but, rather, cokes.

The terms and expressions which have been employed are used as terms ofdescription and not of limitation, and there is no intention that in theuse of such terms and expressions of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of theinvention claimed. Thus, it should be understood that although thepresent invention has been specifically disclosed by preferredembodiments and optional features, modification and variation of theconcepts herein disclosed may be resorted to by those of ordinary skillin the art, and that such modifications and variations are considered tobe within the scope of this invention as defined by the appended claims.

Additional Embodiments

The present invention provides for the following exemplary embodiments,the numbering of which is not to be construed as designating levels ofimportance:

Embodiment 1 provides a method of reducing the pollutant content in apollutant-containing gas, the method comprising: obtaining or providingan activated carbon sorbent comprising activated carbon sorbentparticles comprising nitrogen in a surface layer of the sorbentparticles; contacting a pollutant-containing gas with the activatedcarbon sorbent, to form a pollutant-sorbent composition; and separatingat least some of the pollutant-sorbent composition from thepollutant-containing gas, to give a separated gas.

Embodiment 2 provides the method of Embodiment 1, wherein the pollutantcomprises mercury, and the pollutant-containing gas is amercury-containing gas.

Embodiment 3 provides the method of any one of Embodiments 1-2, whereinthe concentration of nitrogen in the surface layer of the sorbentparticles is higher than the concentration of nitrogen in a core of thesorbent particles.

Embodiment 4 provides the method of any one of Embodiments 2-3, whereinthe activated carbon sorbent combines with at least about 70 wt % of themercury present in the mercury-containing gas.

Embodiment 5 provides the method of any one of Embodiments 2-4, whereinthe mercury-containing gas further comprises a concentration ofsulfur(VI) and the concentration of sulfur(VI) in the mercury-containinggas is greater than about 3 ppm by mole and the activated carbon sorbentforms a mercury-sorbent composition at a higher absorption rate relativeto a corresponding activated carbon sorbent comprising at least one ofa) less or substantially no nitrogen in a corresponding particle surfacelayer, b) less or substantially no halide- or halogen-promotion, whereinthe activated carbon sorbent comprising the activated carbon sorbentparticles is halide- or halogen-promoted, and c) less or substantiallyno inorganic matrix support, wherein the activated carbon sorbentcomprising the activated sorbent particles is inorganicmatrix-supported.

Embodiment 6 provides the method of any one of Embodiments 1-5, whereinthe pollutant-containing gas further comprises a concentration ofsulfur(VI) and the concentration of sulfur(VI) in thepollutant-containing gas is about 3 ppm -2000 ppm.

Embodiment 7 provides the method of any one of Embodiments 1-6, whereinthe nitrogen is substantially homogenously distributed in the core ofthe activated carbon sorbent particles.

Embodiment 8 provides the method of any one of Embodiments 1-7, whereinthe nitrogen in the surface layer decreases neutralization ofcarbocations in the activated carbon by at least one of SO₃ ²⁻ and HSO₃¹⁻, as compared to a corresponding activated carbon sorbent comprisingless or substantially no nitrogen in a corresponding particle surfacelayer.

Embodiment 9 provides the method of any one of Embodiments 1-8, whereinthe nitrogen in the surface layer at least partially blocks carbocationsin the activated carbon from at least one of SO₃ ²⁻ and HSO₃ ¹⁻, ascompared to a corresponding activated carbon sorbent comprising less orsubstantially no nitrogen in a corresponding particle surface layer.

Embodiment 10 provides the method of any one of Embodiments 1-9, furthercomprising: obtaining or providing an unpromoted carbon sorbent;obtaining or providing a promoter; and promoting at least a portion ofthe unpromoted sorbent by contacting the portion of the unpromotedsorbent with the promoter to form the activated carbon sorbent.

Embodiment 11 provides the method of Embodiment 10, wherein the promotercomprises a halogen or halide promoter.

Embodiment 12 provides the method of any one of Embodiments 10-11,wherein the promoter comprises at least one of a halogen, a Group Vhalide, a Group VI halide, a hydrogen halide, an ammonium halide, analkali earth metal halide, and an alkaline earth metal halide.

Embodiment 13 provides the method of any one of Embodiments 10-12,wherein the promoter comprises at least one of HI, Mr, ICl NH₄Br, NaBr,CaBr₂, HBr, NaCl, CaCl₂, and HCl.

Embodiment 14 provides the method of any one of Embodiments 10-13,wherein the promoter is in a form comprising at least one of a vaporform, in a solvent, as a liquid, as a solid, and a combination thereof.

Embodiment 15 provides the method of any one of Embodiments 10-14,wherein the promoting occurs in an aqueous scrubber, wherein thescrubber comprises an aqueous slurry that comprises the promotor.

Embodiment 16 provides the method of any one of Embodiments 1-15,wherein contacting the pollutant-containing gas with the activatedcarbon sorbent comprises adding the activated carbon sorbent into thepollutant-containing gas.

Embodiment 17 provides the method of any one of Embodiments 1-16,wherein the activated carbon sorbent is at least one of in a fixed bed,in a moving bed, in a scrubber, in a filter, or suspended in thepollutant-containing gas.

Embodiment 18 provides the method of any one of Embodiments 1-17,wherein the core of the activated carbon sorbent particles compriseabout 0 wt %-about 99 wt % nitrogen.

Embodiment 19 provides the method of any one of Embodiments 1-18,wherein the core of the activated carbon sorbent particles compriseabout 1 wt %-about 6 wt % nitrogen.

Embodiment 20 provides the method of any one of Embodiments 1-19,wherein the surface layer of the activated carbon sorbent particlescomprises about 0.001 wt %-about 99 wt % nitrogen.

Embodiment 21 provides the method of any one of Embodiments 1-20,wherein the surface layer of the activated carbon sorbent particlescomprises about 5 wt %-about 80 wt % nitrogen.

Embodiment 22 provides the method of any one of Embodiments 1-21,wherein the surface layer of the activated carbon sorbent comprises alayer at the surface of the particle having a thickness of about 0.001%to about 99% of the radius of the particles.

Embodiment 23 provides the method of any one of Embodiments 1-22,wherein the surface layer of the activated carbon sorbent particlescomprises a layer at the surface of the particles having a thickness ofabout 0.001% to about 50% of the radius of the particles.

Embodiment 24 provides the method of any one of Embodiments 1-23,wherein the activated carbon sorbent particles have an average diameterof about 0.1 μm to about 1000 μm.

Embodiment 25 provides the method of any one of Embodiments 1-24,wherein the surface layer of the sorbent particles is a continuoussurface layer.

Embodiment 26 provides the method of any one of Embodiments 1-25,wherein obtaining or providing the activated carbon sorbent comprises:obtaining or providing a carbon precursor comprising nitrogen; andprocessing the carbon precursor with at least one of heating,microwaving, and irradiating, to provide the activated carbon sorbent.

Embodiment 27 provides the method of Embodiment 26, wherein the carbonprecursor comprises a carbonaceous material comprising carbon and anitrogenous material comprising nitrogen.

Embodiment 28 provides the method of Embodiment 27, wherein thecarbonaceous material comprises at least one of brown sugar, barleysugar, caramel, cane sugar, corn syrup, starch, molasses, a glucan, agalactan, a xylan, and a sugar waste product.

Embodiment 29 provides the method of any one of Embodiments 27-28,wherein the nitrogenous material comprises a nitrogen-containing organicor inorganic compound.

Embodiment 30 provides the method of any one of Embodiments 27-29,wherein the nitrogenous material comprises a nitrogen heterocycle, anitrogen-containing polymer or copolymer, a nitrile, a carbamate, anamino acid, nitrobenzene, hydroxylamine, urea, hydrazine, sulfamic acid,or a combination thereof.

Embodiment 31 provides the method of any one of Embodiments 26-30,further comprising: obtaining or providing a substrate material;contacting the carbon precursor and the substrate material, to provide asorbent starting material; and processing the sorbent starting materialwith at least one of heating, microwaving, and irradiating, to providethe activated carbon sorbent.

Embodiment 32 provides the method of Embodiment 31, wherein heating thesorbent starting material provides a second sorbent starting material,further comprising reacting the second sorbent starting material with anacidic or basic material, to provide the activated carbon sorbent.

Embodiment 33 provides the method of any one of Embodiments 31-32,wherein the substrate comprises at least one of diatomaceous earth, aclay, a zeolite, or a mineral.

Embodiment 34 provides the method of any one of Embodiments 31-33,wherein heating the sorbent starting material comprises heating to about100° C.-about 1200° C.

Embodiment 35 provides the method of any one of Embodiments 31-34wherein the activated carbon sorbent comprises a carbon nanocompositesorbet.

Embodiment 36 provides the method of any one of Embodiments 1-35,wherein the activated carbon sorbent comprises one or more bindingsites.

Embodiment 37 provides the method of Embodiment 36, wherein at least aportion of the binding sites in the activated carbon sorbent react withat least one of the pollutant and the oxidized species of the pollutant,to form the pollutant-sorbent composition.

Embodiment 38 provides the method of any one of Embodiments 1-37,wherein the separating at least some of the pollutant-sorbentcomposition from the pollutant containing gas comprises separating in aparticulate separator.

Embodiment 39 provides the method of Embodiment 38, wherein theparticulate separator comprises an electrostatic precipitator (ESP), abaghouse, a wet scrubber, a filter, cyclone, fabric separator, or anycombination thereof.

Embodiment 40 provides the method of any one of Embodiments 10-39,wherein a promoter precursor transforms into the halogen or halidepromoter which then reacts with the activated carbon sorbent to give theactivated carbon material.

Embodiment 41 provides the method of Embodiment 40, wherein the promoterprecursor is at least one of on the unpromoted sorbent and added withthe unpromoted sorbent.

Embodiment 42 provides the method of any one of Embodiments 1-41,further comprising at least one of during and prior to the contactingadding an alkaline component into the pollutant-containing gas.

Embodiment 43 provides the method of Embodiment 42, wherein the alkalinecomponent comprises at least one of an oxide, hydroxide, carbonate, orphosphate of an alkali element, an alkali or alkaline-earth element, anda compound or material including the same.

Embodiment 44 provides the method of any one of Embodiments 1-43,wherein the activated carbon sorbent comprises a stabilizing agentcomprising at least one of S, Se, or mixtures thereof.

Embodiment 45 provides the method of any one of Embodiments 1-44,wherein the activated carbon sorbent comprises a stabilizing agentcomprising at least one of H₂S, SO₂, H₂Se, SeO₂, CS₂, P₂S₅, or mixturesthereof.

Embodiment 46 provides the method of any one of Embodiments 1-45,further comprising regenerating the pollutant-sorbent composition togive a regenerated activated carbon sorbent.

Embodiment 47 provides the method of any one of Embodiments 1-46,wherein the activated carbon sorbent is a generated activated carbonsorbent

Embodiment 48 provides the method of any one of Embodiments 1-47,wherein at least one of the contacting and the separating occurs in anaqueous scrubber.

Embodiment 49 provides the method of Embodiment 48, wherein the scrubbercomprises an aqueous slurry that comprises the activated carbon sorbent.

Embodiment 50 provides a method for reducing the mercury content of amercury-containing gas, the method comprising: obtaining or providing acarbon precursor comprising nitrogen; obtaining or providing a substratematerial; contacting the carbon precursor and the substrate material, toprovide an inorganic matrix-supported sorbent starting material; heatingthe inorganic matrix-supported sorbent starting material, to provide anunpromoted sorbent; promoting at least a portion of the unpromotedsorbent by chemically reacting the portion of the unpromoted sorbentwith a promoter to form a promoted inorganic matrix-supported activatedcarbon sorbent comprising activated carbon sorbent particles comprisingnitrogen in a surface layer of the sorbent particles; contacting amercury-containing gas with the activated carbon sorbent, to form amercury-sorbent composition; and separating at least some of themercury-sorbent composition from the mercury-containing gas, to give aseparated gas; wherein the mercury-containing gas has a concentration ofsulfur(VI) of about 3-2000 ppm by mole and a first quantity theactivated carbon sorbent forms a mercury-sorbent composition at a firstmercury adsorption rate, wherein the first adsorption rate is higherthan a mercury absorption rate of the first quantity of a correspondingactivated carbon sorbent comprising at least one of a) less orsubstantially no nitrogen in a corresponding particle surface layer, b)less or substantially no halide- or halogen-promotion, and c) less orsubstantially no inorganic matrix support.

Embodiment 51 provides a method of making an activated carbon sorbent,comprising: obtaining or providing an unpromoted carbon sorbentcomprising nitrogen; promoting at least a portion of the unpromotedsorbent by contacting the portion of the unpromoted sorbent with apromoter to form an activated carbon sorbent comprising activated carbonsorbent particles comprising nitrogen, wherein the concentration ofnitrogen in a surface layer of the sorbent particles is higher than theconcentration of nitrogen in a core of the sorbent particles.

Embodiment 52 provides the method of Embodiment 51, further comprising:obtaining or providing a carbon precursor comprising nitrogen; obtainingor providing a substrate material; contacting the carbon precursor andthe substrate material, to provide a sorbent starting material; andprocessing the sorbent starting material, to provide the unpromotedcarbon sorbent comprising nitrogen.

Embodiment 53 provides the method of Embodiment 52, wherein obtaining orproviding the carbon precursor comprising nitrogen comprises: obtainingor providing a carbonaceous material comprising carbon and a nitrogenousmaterial comprising nitrogen; and contacting and heating thecarbonaceous material and the nitrogenous material, to provide thecarbon precursor comprising nitrogen.

Embodiment 54 provides a method of making an activated carbon sorbent,comprising: contacting a carbonaceous material and a nitrogenousmaterial, to provide an unpromoted carbon sorbent comprising nitrogen;promoting at least a portion of the unpromoted sorbent by contacting theportion of the unpromoted sorbent with a promoter to form an activatedcarbon sorbent comprising activated carbon sorbent particles comprisingnitrogen, wherein the concentration of nitrogen in the sorbent particlesis higher than the concentration of nitrogen in the carbonaceousmaterial.

Embodiment 55 provides an activated carbon sorbent made by the method ofany one of Embodiments 51-54.

Embodiment 56 provides an activated carbon sorbent, comprising: ahalogen- or halide-promoted activated carbon, the activated carboncomprising activated carbon sorbent particles comprising nitrogen in asurface layer of the sorbent particles.

Embodiment 57 provides the activated carbon sorbent of Embodiment 56,wherein the concentration of nitrogen in the surface layer of thesorbent particles is higher than the concentration of nitrogen in a coreof the sorbent particles.

Embodiment 58 provides the activated carbon sorbent of any one ofEmbodiments 56-57, wherein the activated carbon sorbent particles havean average diameter of about 0.1 μm to about 1000 μm.

Embodiment 59 provides the activated carbon sorbent of any one ofEmbodiments 56-58, wherein the activated carbon is at least one ofhalogen-promoted, Group V halide-promoted, Group VI halide-promoted,hydrogen halide-promoted, ammonium halide-promoted, alkali earth metalhalide-promoted, and alkaline earth metal halide-promoted.

Embodiment 60 provides the activated carbon sorbent of any one ofEmbodiments 56-59, wherein the activated carbon sorbent is inorganicmatrix-supported, the inorganic matrix support comprising at least oneof diatomaceous earth, a clay, a zeolite, or a mineral.

Embodiment 61 provides the activated carbon sorbent of any one ofEmbodiments 56-60, wherein the nitrogen is substantially homogenouslydistributed in the core of the activated carbon sorbent particles.

Embodiment 62 provides the activated carbon sorbent of any one ofEmbodiments 56-61, wherein the nitrogen in the surface layer of theparticles at least partially decreases neutralization by HSO₃ ¹⁻ or SO₃²⁻ of carbocations in the activated carbon sorbent, as compared to acorresponding activated carbon sorbent comprising less or substantiallyno nitrogen in a corresponding particle surface layer undersubstantially similar conditions.

Embodiment 63 provides the activated carbon sorbent of any one ofEmbodiments 56-62, wherein the nitrogen in the surface layer of theparticles at least partially blocks carbocations in the activated carbonfrom forming ionic bonds with HSO₃ ¹⁻ or SO₃ ²⁻, as compared to acorresponding activated carbon sorbent comprising less or substantiallyno nitrogen in a corresponding particle surface layer undersubstantially similar conditions.

Embodiment 64 provides the activated carbon sorbent of any one ofEmbodiments 56-63, wherein a first quantity of the activated carbonsorbent forms a mercury-sorbent composition at a first mercuryadsorption rate in a gas composition comprising mercury wherein theconcentration of sulfur(VI) in the gas composition is about 3-2000 ppmby mole, and wherein the first adsorption rate is higher than a mercuryabsorption rate of the first quantity of a corresponding activatedcarbon sorbent comprising at least one of a) less or substantially nonitrogen in a corresponding particle surface layer, b) less orsubstantially no halide- or halogen-promotion, and c) less orsubstantially no inorganic matrix support, wherein the activated carbonsorbent is inorganic-matrix supported.

Embodiment 65 provides the activated carbon sorbent of any one ofEmbodiments 56-64, wherein the nitrogen is derived from anitrogen-containing organic or inorganic compound.

Embodiment 66 provides the activated carbon sorbent of any one ofEmbodiments 56-65, wherein the nitrogen is derived from indole,quinoxaline, carbazole, isoquinoline, nitrobenzene, urea, sulfamic acid,polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer,vinylpyrrolidone-acrylic acid copolymer, vinylpyrrolidone-maleic acidcopolymer, polyethylenimine, alanine, piperazine, quinolone,quinoxaline, diazabicyclooctane, an amino acid, an ammonium salt, or acombination thereof.

Embodiment 67 provides an activated carbon sorbent for use in mercuryremoval from a mercury-containing gas, the sorbent comprising: ahalogen- or halide-promoted activated carbon comprising activated carbonparticles, the particles comprising nitrogen in a surface layer, thenitrogen in the surface layer at sufficient concentration to at leastone of a) decrease neutralization by HSO₃ ¹⁻ or SO₃ ²⁻ of carbocationsin the activated carbon sorbent, as compared to a correspondingactivated carbon sorbent comprising less or substantially no nitrogen ina corresponding particle surface layer under substantially similarconditions, and b) at least partially block carbocations in theactivated carbon from forming ionic bonds with HSO₃ ¹⁻ or SO₃ ²⁻, ascompared to a corresponding activated carbon sorbent comprising less orsubstantially no nitrogen in a corresponding particle surface layerunder substantially similar conditions.

Embodiment 68 provides the apparatus or method of any one or anycombination of Embodiments 1-67 optionally configured such that allelements or options recited are available to use or select from.

What is claimed is:
 1. Halogen- or halide-promoted activated carbon sorbent particles comprising nitrogen in a surface layer thereof, wherein the nitrogen is derived from an ammonium salt.
 2. The promoted activated sorbent particles of claim 1, wherein the concentration of nitrogen in the surface layer of the sorbent particles is higher than the concentration of nitrogen in a core of the sorbent particles.
 3. The promoted activated sorbent particles of claim 1, wherein the core of the activated carbon sorbent particles is about 0 wt % to about 99 wt % nitrogen.
 4. The promoted activated sorbent particles of claim 1, wherein the surface layer of the activated carbon sorbent particles is about 0.001 wt % to about 99 wt % nitrogen.
 5. The promoted activated sorbent particles of claim 1, wherein the surface layer of the activated carbon sorbent particles comprises a layer at the surface of the particles independently having a thickness of about 0.001% to about 99% of the radius of the particles.
 6. The promoted activated sorbent particles of claim 1, wherein the surface layer of the activated carbon sorbent particles comprises a layer at the surface of the particles having a thickness of about 0.001% to about 50% of the radius of the particles.
 7. The promoted activated sorbent particles of claim 1, wherein the activated carbon sorbent particles have an average diameter of about 0.1 μm to about 1000 μm.
 8. A method of reducing the mercury content in a mercury-containing gas, the method comprising: contacting a mercury-containing gas with the promoted activated carbon sorbent particles of claim 1, to form a mercury-sorbent composition; and separating at least some of the mercury-sorbent composition from the mercury-containing gas, to give a separated gas.
 9. The method of claim 8, wherein the mercury-containing gas further comprises a concentration of sulfur(VI) and the concentration of sulfur(VI) in the mercury-containing gas is greater than or equal to about 1 ppm by mole and the promoted activated carbon sorbent particles form a mercury-sorbent composition at a higher absorption rate relative to corresponding promoted activated carbon sorbent particles comprising at least one of a) less or substantially no nitrogen in a corresponding particle surface layer, b) less or substantially no halide- or halogen-promotion.
 10. The method of claim 8, further comprising: promoting unpromoted activated carbon sorbent particles, to provide the halogen- or halide-promoted activated carbon sorbent particles.
 11. The method of claim 10, wherein the promoting comprises contacting the unpromoted activated carbon sorbent particle with a promoter or a promoter precursor that transforms into the promoter.
 12. The method of claim 11, wherein the promoter comprises at least one of a halogen, a Group V halide, a Group VI halide, a hydrogen halide, an ammonium halide, an alkali earth metal halide, and an alkaline earth metal halide.
 13. The method of claim 11, wherein the promoter comprises at least one of F₂, F⁻, Cl₂, Cl⁻, Br₂, Br⁻, I₂, I⁻, HI, IBr, ICl, NH₄Br, NaBr, CaBr₂, HBr, NaCl, CaCl₂, and HCl, the promoter precursor comprises at least one of NH₄Br, NaBr, CaBr₂, NH₄Cl, NaCl, CaCl₂, NH₄F, NaF, and CaF₂, or a combination thereof.
 14. The method of claim 10, wherein the promotion is performed in the mercury-containing gas.
 15. The method of claim 14, wherein the promoting comprises contacting the unpromoted activated carbon sorbent particle with a promoter or a promoter precursor that is added as a gas, liquid, solid, or combination thereof, to the mercury-containing gas stream or to coal that is burned to form the mercury-containing gas stream.
 16. The method of claim 10, further comprising: processing a mixture comprising a carbon precursor and the ammonium salt or a decomposition product thereof, to provide the unpromoted activated carbon sorbent particles.
 17. The method of claim 16, wherein the processing comprises at least one of heating to about 100° C. to about 15,000° C., microwaving, and irradiating.
 18. The method of claim 16, wherein the processing is performed in the mercury-containing gas.
 19. A method of making activated carbon sorbent particles, the method comprising: heating a mixture comprising a carbon precursor and the ammonium salt or a degradation product thereof, to provide activated carbon sorbent particles.
 20. A method of making the promoted activated carbon sorbent particles of claim 1, the method comprising: heating a mixture comprising a carbon precursor and the ammonium salt or a degradation product thereof, to provide unpromoted activated carbon sorbent particles; and promoting the unpromoted activated carbon sorbent particles, to provide the halogen- or halide-promoted activated carbon sorbent particles. 